Phenolfree stabilization of polyolefins

ABSTRACT

The instant invention relates to stabilizer compositions for thermoplastic polymers comprising a) at least one organophosphine, b) at least one 2-phenylbenzofuranone, and c) at least one sterically hindered piperidine based stabilizer (HAS), wherein the weight ratio of component a) to component b) to component c) is from 1:0.05:0.5 to 1:3:5. The instant compositions need an overall lower concentration as compared with the conventional phenol-containing formulations. In polyolefin articles, particularly in polyolefin-fibers, discoloration during processing and service life by both the formation of quinoid products and by action of NOx gases (gasfading) is avoided.

[0001] The instant invention relates to stabilizing compositions whichare free from phenolic antioxidants for polyolefins, especially forpolypropylene.

[0002] Polyolefin-articles and especially polyolefin-fibers are amongthe most typical examples demonstrating the need of stabilization forthe successful use of synthetic raw materials. Polypropylene requiresprotection during its entire life cycle. Particularly polypropylenefibers need special attention since processing takes usually place athigher temperatures as applied for other polypropylene articles,typically at 270-300° C.

[0003] Conventional stabilization packages consist of phenolicantioxidants used in combination with organo-phosphites and-phosphonites to provide adequate processing stability and to ensurelong-term protection against thermooxidative degradation. For the latterphosphites and phosphonites do not contribute significantly.

[0004] Since many years it is known from the literature thatpiperidine-based stabilizers (HAS), particularly high molecular mass HAScontribute to long term heat protection of polypropylene. Usually thetime to failure of polypropylene fibers increases with the HASconcentration in a non-linear manner.

[0005] On the other hand it is well known that discoloration of polymerscontaining sterically hindered phenolic antioxidants, which are used asprimary antioxidants for long-term heat protection, takes place byformation of colored transformation products of these additivescontaining quinoid structures. Its extent depends on structure andconsumption of phenols. Generally, discoloration of polyolefins isparticularly pronounced by continuous contact with water or NO_(x)-gases(F. Gugumus, chapter “Antioxidants” in Plastics Additives, editors R.Gächter and H. Müller, Hanser Publishers, Munich, Vienna, New York,3^(rd) edition, pages 1-104 (1990) and P. P. Klemchuk and P.-L. Horng,Polym. Degrad. Stab., Vol. 34, pp. 333 (1991)).

[0006] These effects and observations initiated new stabilizationconcepts to abandon sterically hindered phenols from use forstabilization of polyolefins and especially of polypropylene fibers. Newgeneration of stabilizers are now commercially available which allowprocessing at high temperatures as applied for the manufacture ofpolypropylene fibers.

[0007] Known are stabilizer systems, which consist of anorganophosph(on)ite, a benzofuranone-based, component andpiperidine-based HAS compounds for phenol-free stabilization purposes.GB-A-2 315 070 discloses stabilizer mixtures for organic materialcomprising at least one compound of the benzofuran-2-one type and atleast one compound of the sterically hindered amine type, an organicphosphite or phosphonite may also be included in the stabilizer mixture.

[0008] It is the object of the present invention to provide an improvedstabilizer composition for the stabilization of polyolefin polymerswherein phenolic antioxidants are not necessary.

[0009] This object is achieved with the stabilizer composition ashereunder described. It has now been found that appropriate phenol-freestabilizer systems used in a certain ratio as defined below fulfill thegiven technical requirements for processing of polyolefins, particularlyfor processing of polyolefin fibers under distinct improvement ofmaintenance of both the molecular weight as well as of color if comparedagainst conventional phenol-containing stabilizer formulations.

[0010] These additive systems consist basically of an organophosphineand a 2-phenylbenzofuranone (“lactone”) and a sterically hinderedpiperidine-based stabilizer (HAS).

[0011] Accordingly the present invention provides a stabilizercomposition comprising

[0012] a) at least one organophosphine,

[0013] b) at least one 2-phenylbenzofuranone, and

[0014] c) at least one sterically hindered piperidine based stabilizer(HAS),

[0015] wherein the weight ratio of component a) to component b) tocomponent c) is from 1:0.05:0.5 to 1:3:5.

[0016] Preferably the invention provides a stabilizer compositioncomprising

[0017] a) at least one compound of the formulae (I) to (IV) [hereinbelow referred to as component a)]

[0018]  in which independently of one another

[0019] R₁ is C₁₋₂₄-alkyl or C₁₋₂₄-N,O,P,S-heteroalkyl; C₅₋₃₀-cycloalkylor C₅₋₃₀-N,O,P,S-heterocycloalkyl; C₇₋₃₀-alkylaryl; C₆₋₂₄-aryl;C₄₋₂₄-N,O,P,S-heteroaryl; C₆₋₂₄-aryl or C₄₋₂₄-N,O,P,S-heteroaryl mono-or polysubstituted by C₁₋₁₈-alkyl, C₅₋₁₂-cycloalkyl or by C₁₋₁₈-alkoxygroups;

[0020] R₂ is C₄₋₂₄-alkyl or C₄₋₂₄-N,O,P,S-heteroalkyl; C₅₋₃₀-cycloalkylor C₅₋₃₀-N,O,P,S-heterocycloalkyl; C₇₋₃₀-alkylaryl; C₆₋₂₄-aryl;C₄₋₂₄-N,O,P,S-heteroaryl; C₆₋₂₄-aryl or C₄₋₂₄-N,O,P,S-heteroaryl mono-or polysubstituted by C₁₋₁₈-alkyl, by C₅₋₁₂-cycloalkyl or byC₁₋₁₈-alkoxy groups;

[0021] D is C₁₋₃₀-alkylene or C₁₋₃₀-N,O,P,S-alkylene, linear orbranched; C₂₋₃₀-alkylidene or C₂₋₃₀-N,O,P,S-alkylidene;C₅₋₁₂-cycloalkylene or C₅₋₁₂-N,O,P,S-cycloalkylene; C₆₋₂₄-arylene orC₄₋₂₄-N,O,P,S-heteroarylene, unsubstituted or one- or morefoldsubstituted by linear or branched C₁₋₁₈-alkyl, by C₅₋₁₂-cycloalkyl or byC₁₋₁₈-alkoxy; or —O—, —S—;

[0022] q is 1 to 5;

[0023] r is 3 to 6, where the groups P—R₁ in the formula (IV) are acomponent of a phosphacycle, indicated by * in the bonds originatingfrom P;

[0024] b) at least one compound which can be described by the formula V(referred to as component b)

[0025]  in which

[0026] R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) independentlyof one another are hydrogen; hydroxyl; C₁-C₁₈-alkyl; or phenyl which isunsubstituted or mono-, di- or tri-substituted by C₁-C₄-alkyl; areC₇-C₉-phenylalkyl, C₁-C₁₈-alkoxy or C₅-C₁₂-cycloalkyl unsubstituted ormono-, di- or trisubstituted by C₁-C₄-alkyl; and R^(c) has one of themeanings given above for R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) andR^(h) or is a radical of the formula (VI)

[0027]  in which

[0028] R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) are as definedabove and R^(i) and R^(j) independently of one another are hydrogen orC₁-C₄-alkyl, where at least two of the radicals R^(d), R^(e), R^(f),R^(g) and R^(h) are hydrogen; and

[0029] c) at least one sterically hindered amine of the formula VII(referred to as component c),

[0030]  in which

[0031] X₁ is hydrogen; a C₁-C₂₂-alkyl group; an oxygen radical O*; —OH;—NO; —CH₂CN; benzyl; allyl; a C₁-C₃₀-alkoxy group; aC₅-C₁₂-cycloalkyloxy group; a C₆-C₁₀-aryloxy group; aC₇-C₂₀-arylalkyloxy group or a C₇-C₂₀-arylalkyloxy group where the arylradical is substituted by a C₁-C₅-alkyl group or a halogen or a nitrogroup; a C₃-C₁₀-alkenyl group; a C₃-C₆-alkinyl group; a C₁-C₁₀-acylgroup; halogen; an unsubstituted or C₁-C₄-alkyl-substituted phenylradical;

[0032] X₂ is hydrogen; a [CH₂—CH₂—C(O)—O—X₅] radical; a[CH₂—C(CH₃)H—C(O)—O—X₅] radical; a C₁-C₂₂-alkyl group;

[0033] X₃ and X₄ independently of one another are hydrogen; anunsubstituted or C₁-C₄-alkyl-substituted phenyl radical; or aC₁-C₂₂-alkyl group, where at least one of the two radicals X₃ and X₄ isa branched C₄-C₂₂-alkyl group; and in which

[0034] X₅ is a C₁-C₂₂-alkyl group.

[0035] The alkyl groups as mentioned above may be linear or branched.

[0036] Preference is given to components wherein

[0037] R₁ is C₈₋₂₄-alkyl or C₈₋₂₄-N,O,P,S-heteroalkyl; C₆₋₁₂-cycloalkylor C₆₋₁₂-N,O,P,S-heterocycloalkyl; C₇₋₂₄-alkylaryl; C₆₋₁₆-aryl;C₄₋₁₈-N,O,P,S-heteroaryl; C₆₋₁₆-aryl or C₄₋₁₈-N,O,P,S-heteroaryl mono-or polysubstituted by C₁₋₁₂-alkyl, by C₅₋₈-cycloalkyl or by C₁₋₁₂-alkoxygroups;

[0038] R₂ is C₆₋₁₈-alkyl or C₆₋₁₈-N,O,P,S-heteroalkyl; C₅₋₁₂-cycloalkylor C₅₋₁₂-N,O,P,S-heterocycloalkyl; C₇₋₁₈-alkylaryl; C₆₋₁₆-aryl;C₄₋₈-N,O,P,S-heteroaryl; C₆₋₁₆-aryl or C₄₋₁₈-N,O,P,S-heteroaryl mono- orpolysubstituted by C₁₋₁₂-alkyl, by C₅₋₈-cycloalkyl or by C₁₋₁₂-alkoxygroups;

[0039] D is C₁₋₂₄-alkylene or C₁₋₂₄-N,O,P,S-alkylene, linear orbranched; C₂₋₂₄-alkylidene or C₂₋₂₄-N,O,P,S-alkylidene;C₅₋₈-cycloalkylene or C₅₋₈-N,O,P,S-cycloalkylene; C₆₋₂₄-arylene orC₄₋₁₈-N,O,P,S-heteroarylene, unsubstituted or one- or morefoldsubstituted by linear or branched C₁₋₁₈-alkyl, by C₅₋₈-cycloalkyl or byC₁₋₁₂-alkoxy; or —O—; —S—;

[0040] q is 1 to 4;

[0041] r is 4 or 5, where the groups P—R₁ in the formula (IV) arecomponent of a phosphacycle, indicated by * in the bonds originatingfrom P;

[0042] R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) independentlyof one another are hydrogen; hydroxyl; C₁-C₁₂-alkyl; or phenyl which isunsubstituted or mono-, di- or trisubstituted by C₁-C₂-alkyl; areC₇-C₉-phenylalkyl; C₁-C₁₂-alkoxy or C₅-C₈-cycloalkyl unsubstituted ormono-, di- or trisubstituted by C₁-C₂-alkyl; and R^(c) has one of themeanings given above for R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) andR^(h) or is a radical of the formula (VI) in which

[0043] R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) are as definedabove and R^(i) and R^(j) independently of one another are hydrogen orC₁-C₂-alkyl, where at least two of the radicals R^(d), R^(e), R^(f),R^(g) and R^(h) are hydrogen;

[0044] X₁ is hydrogen; a C₁-C₅-alkyl group; an oxygen radical O*; —OH;—NO; —CH₂CN;

[0045] benzyl; allyl; a C₁-C₁₀-alkoxy group; a C₅-C₆-cycloalkyloxygroup; a C₆-C₇-aryloxy group; a C₇-C₁₀-arylalkyloxy group or aC₇-C₁₀-arylalkyloxy group where the aryl radical is substituted by aC₁-C₅-alkyl group or a halogen or a nitro group; a C₃-C₆-alkenyl group;a C₃-C₆-alkinyl group; a C₁-C₅-acyl group; halogen; an unsubstituted orC₁-C₂-alkyl-substituted phenyl radical;

[0046] X₂ is hydrogen; a [CH₂—CH₂—C(O)—O—X₅] radical; a[CH₂—C(CH₃)H—C(O)—O—X₅] radical; a C₁-C₁₀-alkyl group;

[0047] X₃ and X₄ independently of one another are hydrogen; anunsubstituted or C₁-C₂-alkyl-substituted phenyl radical or a branchedC₄-C₂₂-alkyl group, where at least one of the two radicals X₃ and X₄ isa branched C₄-C₁₀-alkyl group; and in which

[0048] X₅ is a C₁₀-C₁₆-alkyl group.

[0049] Particular preference is given to compounds wherein

[0050] R₁ is C₁₂₋₁₆-alkyl or C₁₂₋₁₆-N,O,P,S-heteroalkyl; C₆₋₈-cycloalkylor C₆₋₈-N,O,P,S-heterocycloalkyl; C₇₋₁₂-alkylaryl; C₆₋₁₂₋aryl orC₄₋₁₀-N,O,P,S-heteroaryl; C₆₋₁₂-aryl or C₄₋₁₀-heteroaryl mono- orpolysubstituted by C₁₋₁₈-alkyl, by C₅₋₆-cycloalkyl or by C₁₋₈-alkoxygroups;

[0051] R₂ is C₈₋₁₈-alkyl or C₈₋₁₈-N,O,P,S-heteroalkyl; C₅₋₈-cycloalkylor C₅₋₈-N,O,P,S-heterocycloalkyl; C₇₋₁₂-alkylaryl; C₆₋₁₂-aryl;C₄₋₁₀-N,O,P,S-heteroaryl; C₆₋₁₂-aryl or C₄₋₁₀-N,O,P,S-heteroaryl mono-or polysubstituted by C₁₋₈-alkyl, by C₅₋₆-cycloalkyl or by C₁₋₈-alkoxygroups;

[0052] D is C₁₋₁₈-alkylene or C₁₋₁₈-N,O,P,S-alkylene, linear orbranched; C₂₋₁₈-alkylidene or C₂₋₁₈-N,O,P,S-alkylidene;C₅₋₈-cycloalkylene or C₅₋₈-N,O,P,S-cycloalkylene; C₆₋₁₈-arylene orC₄₋₁₈-N,O,P,S-heteroarylene, unsubstituted or one- or morefoldsubstituted by linear or branched C₁₋₁₂-alkyl, by C₅₋₈-cycloalkyl or byC₁₋₈-alkoxy; or —O—; —S—;

[0053] q is 1 to 3;

[0054] r is 4 o 5, where the groups P—R₁ in the formula (IV) arecomponent of a phosphacycle, indicated by * in the bonds originatingfrom P,

[0055] R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) independentlyof one another are hydrogen; hydroxyl; C₁-C₆-alkyl; or phenyl which isunsubstituted or mono-, di- or trisubstituted by C₁-C₂-alkyl; areC₇-C₉-phenylalkyl; C₁-C₆-alkoxy or C₅-C₈-cycloalkyl unsubstituted ormono-, di- or trisubstituted by C₁-C₂-alkyl; and R^(c) has one of themeanings given above for R^(a), R^(b), R^(d), R^(f), R^(e), R^(g) andR^(h) or is a radical of the formula (VI) in which

[0056] R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) are as definedabove and R^(i) and R^(j) independently of one another are hydrogen orC₁-C₂-alkyl, where at least two of the radicals R^(d), R^(e), R^(f),R^(g) and R^(h) are hydrogen;

[0057] X₁ is hydrogen; a methyl group; an oxygen radical O*; —OH; —NO;—CH₂CN; benzyl; allyl; a C₁-C₆-alkoxy group; a C₅-C₆-cycloalkyloxygroup; a C₆-aryloxy group; a C₃-C₆, alkenyl group; a C₃-C₆-alkinylgroup; a C₁-C₅-acyl group; halogen; an unsubstituted orC₁-C₂-alkyl-substituted phenyl radical;

[0058] X₂ is hydrogen, a [CH₂—CH₂—C(O)—O—X₅] radical, a[CH₂—C(CH₃)H—C(O)—O—X₅] radical, a C₁-C₄-alkyl group;

[0059] X₃ and X₄ independently of one another are hydrogen, anunsubstituted or C₁-C₂-alkyl-substituted phenyl radical or a branchedC₄-C₆-alkyl group, where at least one of the two radicals X₃ and X₄ is abranched C₄-C₆-alkyl group; and in which

[0060] X₅ is a C₁₂-C₁₄-alkyl group.

[0061] Especially preferred is a stabilizer composition comprising

[0062] a) triphenylphosphine,

[0063] b) 2-phenylbenzofuranone and

[0064] c) polymer of epichlorhydrin and2,2,4,4-tetramethyl-7-oxa-3,20-diaza-20-(2,3-epoxi-propyl)-dispiro-[5.1.11.2]-heneicosane-21-one,

[0065] wherein the weight ratio of component a) to component b) tocomponent c) is from 1:0.1:1 to 1:1:3.

[0066] Particularly suitable are the following representatives of thecomponent a):

Component A)

[0067] triphenylphosphane

[0068] tris(2-methylphenyl)phosphane

[0069] tris(4-methylphenyl)phosphane

[0070] tris(2-methoxyphenyl)phosphane

[0071] tris(4-methoxyphenyl)phosphane

[0072] tetracyclohexylcyclotetraphosphane

[0073] tetratert-butylcyclotetraphosphane

[0074] tetrabiphenylcyclotetraphosphane

[0075] tetraphenylcyclotetraphosphane

[0076] pentaphenylcyclopentaphosphane

[0077] pentabiphenylylcyclopentaphosphane

[0078] tetraphenydiphosphane

[0079] tetracyclohexyldiphosphane

[0080] bis(diphenylphosphino)methane

[0081] 1,2-bis(diphenylphosphino)ethane

[0082] 1,3-bis(diphenylphosphino)propane

[0083] 1,4-bis(diphenylphosphino)butane

[0084] 1,5-bis(diphenylphosphino)pentane

[0085] 1,6-bis(diphenylphosphino)hexane

[0086] 1,8-bis(diphenylphosphino)octane

[0087] 1,3-bis(diphenylphosphino)-2,2-dimethylpropane

[0088] 1,1,1-tris(diphenylphosphinomethyl)methane

[0089] 1,1,1-tris(diphenylphosphinomethyl)ethane

[0090] 1,1,1-tris(diphenylphosphinomethyl)propane

[0091] 1,1,1-tris(diphenylphosphinomethyl)butane

[0092] 1,1,1-tris(diphenylphosphinomethyl)-1-phenylmethane

[0093] 1,3-bis(diphenylphosphinomethyl)-2,2-diphenylphosphinopropane

[0094] 1,3-bis(diphenylphosphinomethyl)-2,2-diethylphosphinopropane

[0095] 1,3-bis(diphenylphosphino)-2-methylpropane

[0096] Examples of sterically hindered amines (component c)) are:

[0097] bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate

[0098] bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate

[0099] bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate

[0100] bis(1,2,2,6,6-pentamethyl-4-piperidinyl)succinate

[0101] bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate

[0102] bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)succinate

[0103] bis(1,2,2,6,6-pentamethyl-4-piperidinyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate

[0104]bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate

[0105] tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate

[0106] tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate

[0107] 4-benzoyl-2,2,6,6-tetramethylpiperidine

[0108] 4-stearyloxy-2,2,6,6-tetramethylpiperidine

[0109] a mixture of 4-hexadecyloxy-2,2,6,6-tetramethylpiperidine and4-stearyloxy-2,2,6,6-tetramethylpiperidine

[0110] bis(2,2,6,6-tetramethyl-4-piperidinyl)1,5-dioxaspiro[5.5]undecane-3,3-di-carboxylate

[0111] bis(1,2,2,6,6-pentamethyl-4-piperidinyl)1,5-dioxaspiro[5.5]undecane-3,3-di-carboxylate

[0112]3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione

[0113]8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione

[0114]3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione

[0115] (also N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide)

[0116]3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione

[0117] (also N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide)

[0118]3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione

[0119] (alsoN-(1-acetyl-2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide)

[0120] 1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone)

[0121] the condensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy-piperidine withsuccinic acid or dialkyl succinate

[0122] the condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexa-methylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine

[0123] the condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexa-methylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine

[0124] the condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexa-methylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine

[0125] the condensation product of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetra-methylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane

[0126] the condensation product of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-penta-methylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane

[0127] the condensation product of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-penta-methylpiperidyl)-1,3,5-triazineand 1,6,11-trisaminoundecane

[0128] the reaction product of 1,2-bis(3-aminopropylamino)ethane and2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpiperidine

[0129] the polymer of epichlorhydrin and2,2,4,4-tetramethyl-7-oxa-3,20-diaza-20-(2,3-epoxi-propyl)-dispiro-[5.1.11.2]-heneicosane-21-one.

[0130] Particularly suitable are all mixtures which can be formed bycombining one or more of the components a) to c).

[0131] If compared with the state of the art systems containing amongother stabilizers sterically hindered phenol-based derivatives, the useof the new systems in polyolefin articles, particularly inpolyolefin-fibers, avoids discoloration during processing and servicelife by both the formation of quinoid products and by action of NO_(x)gases (gasfading).

[0132] Another advantage is the use of an overall lower concentration ofstabilizers as compared with the conventional phenol-containingformulations (see example below).

[0133] The concentration of the stabilizer composition amounts from0.001 to 5%, preferably from 0.01 to 1%, more preferably from 0.1 to0.5% by weight, based on the weight of the polymers to be stabilized.

[0134] The polymer can contain other components such as aminoacid-basedprocessing stabilizers, organic and inorganic UV absorbers, acidscavengers, metal desactivators, nucleating agents, fillers, antistaticagents, color improvers, plastizicers, lubricants, metal desactivators,dyes, pigments, emulsifiers, flame retardants, blowing agents,crosslinking agents, antiblocking agents, slip agents, thiosynergistsinorganic carriers such as SiO₂ and processing aids.

[0135] Suitable thermoplastic polymers to be stabilized according to theinstant invention are for example the following ones:

[0136] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forexample of cyclopentene or norbornene; furthermore polyethylene (whichoptionally can be crosslinked); for example, high density polyethylene(HDPE), polyethylene of high density and high molar mass (HDPE-HMW),polyethylene of high density and ultrahigh molar mass (HDPE-UHMW),medium density polyethylene (HMDPE), low density polyethylene (LDPE),linear low density polyethylene (LLDPE), branched low densitypolyethylene (BLDPE).

[0137] Polyolefins, i.e. polymers of mono-olefins exemplified in thepreceding paragraph, in particular polyethylene and polypropylene, canbe prepared by various, and especially by the following, methods:

[0138] a) free-radical polymerization (normally under high pressure andat elevated temperature)

[0139] b) catalytic polymerization using a catalyst that normallycontains one or more metals of group IVb, Vb, VIb or VIII of thePeriodic Table. These metals usually have one or more ligands, such asoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metal,complexes may be in the free form or fixed on substrates, for example onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerizationmedium. The catalysts can be active as such in the polymerization orfurther activators may be used, for example metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyl-oxanes,the metals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified, for example, with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

[0140] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polyethylene withpolyisobutylene, polypropylene with polyethylene (for examplePP/HDPE/LDPE) and mixtures of different types of polyethylene (forexample LDPE/HDPE) with one another.

[0141] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene-propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene-but-1-ene copolymers,propylene-isobutylene copolymers, ethylene-but-1-ene copolymers,ethylene-hexene copolymers, ethylene-methylpentene copolymers,ethylene-heptene copolymers, ethylene-octene copolymers,propylene-butadiene copolymers, isobutylene-isoprene copolymers,ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylatecopolymers, ethylene-vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene-acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedunder 1), for example polypropylene-ethylene-propylene copolymers,LDPE-ethylene-vinyl acetate copolymers, LDPE-ethylene-acrylic acidcopolymers, LLDPE-ethylene-vinyl acetate copolymers,LLDPE-ethylene-acrylic acid copolymers and alternating or randompolyalkylene-carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0142] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifier resins) and mixtures ofpolyalkylenes and starch.

[0143] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0144] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene-butadiene,styrene-acrylonitrile, styrene-alkyl methacrylate,styrene-butadiene-alkyl acrylate, styrene-butadiene-alkyl methacrylate,styrene-maleic anhydride, styrene-acrylonitrile-methacrylate; mixturesof high impact strength of styrene copolymers and another polymer, forexample a polyacrylate, a diene polymer or an ethylene-propylene-dieneterpolymer; and block copolymers of styrene, such asstyrene-butadiene-styrene, styrene-isoprene-styrene,styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

[0145] 7. Graft copolymers of styrene or α-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or alkyl methacrylates on polybutadiene, styrene andacrylonitrile on ethylene-propylene-diene terpolymers, styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate-butadiene copolymers, as well as mixturesthereof with the copolymers mentioned under 6), for example thecopolymer mixtures known as ABS, MBS, ASA or AES polymers.

[0146] 8. Halogen-containing polymers, such as polychloroprene,chlorinated rubber, chlorinated and brominated copolymer ofisobutylene-isoprene (halobutyl ruuber), chlorinated or sulfochlorinatedpolyethylene, copolymers of ethylene and chlorinated ethylene,epichlorohydrin homo- and copolymers, especially polymers ofhalogen-containing vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; aswell as copolymers thereof such as vinyl chloride-vinylidene chloride,vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

[0147] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates,polyacrylonitriles, polyacrylamides and polymethyl methacrylatesimpact-modified with butyl acrylate.

[0148] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile-butadienecopolymers, acrylo-nitrile-alkyl acrylate copolymers,acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinylhalide copolymers or acrylonitrile-alkyl methacrylate-butadieneterpolymers.

[0149] 11. Polymers derived from unsaturated alcohols and amines or theacyl-derivatives or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in section 1.

[0150] 12. Homopolymers and copolymers of cyclic ethers, such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0151] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain comonomers, for example ethylene oxide;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0152] 14. Polyphenylene oxides and sulfides, and mixtures thereof withstyrene polymers or polyamides.

[0153] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters and poly-butadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0154] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, 6, 6/6, 6/10, 6/9, 6/12,4/6, 12/12, 11 and 12, aromatic polyamides starting from m-xylene,diamine and adipic acid; polyamides prepared from hexamethylenediamineand isophthalic and/or terephthalic acid and with or without anelastomer as modifier, for example poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenylene isophthalamide. Block copolymers ofthe aforementioned polyamides with polyolefins, olefin copolymers,ionomers or chemically bonded or grafted elastomers; or with polyethers,e.g. with polyethylene glycol, polypropylene glycol orpolytetramethylene glycol. As well as polyamides or copolyamidesmodified with EPDM or ABS; and polyamides condensed during processing(RIM polyamide systems).

[0155] 17 Polyureas, polyimides, polyamide-imides, polyether imides,polyester amides, polyhydantoins and polybenzimidazoles.

[0156] 18. Polyesters derived from dicarboxylic acids and dialcoholsand/or from hydroxy-carboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, aswell as block polyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

[0157] 19. Polycarbonates and polyester carbonates.

[0158] 20. Polysulfones, polyether sulfones and polyether ketones.

[0159] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, urea or melamine on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0160] 22. Drying and non-drying alkyd resins.

[0161] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and un-saturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0162] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example from epoxy acrylates, urethane acrylates orpolyester acrylates.

[0163] 25. Alkyd resins, polyester resins and acrylic resins crosslinkedwith melamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

[0164] 26. Crosslinked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic or aromatic glycidyl compounds, examplesbeing products of bisphenol A diglycidyl ethers, bisphenol F diglycidylethers, which are crosslinked by means of customary hardeners, such asanhydrides or amines, for example, with or without accelerators.

[0165] 27. Natural polymers such as cellulose, natural rubber, gelatinand derivatives thereof which have been chemically modified in apolymer-homologous manner, for example cellulose acetates, cellulosepropionates and cellulose butyrates, or the cellulose ethers such asmethyl cellulose; as well as rosins and derivatives.

[0166] 28. Mixtures (polyblends) of the aforementioned polymers, forexample PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO,PBT/ABS or PBT/PET/PC.

[0167] 29. Natural and synthetic organic substances which constitutepure monomeric compounds or mixtures thereof, examples being mineraloils, animal or vegetable fats, oils and waxes, or oils, waxes and fatsbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates), and also blends of synthetic esters with mineral oils inany desired proportion by weight, as are employed, for example, as spinfinishes, and aqueous emulsions thereof.

[0168] 30. Aqueous emulsions of natural or synthetic rubbers, such asnatural rubber latex or latices of carboxylated styrene-butadienecopolymers.

[0169] The stabilizer compositions of the instant invention or thethermoplastic polymers to be stabilized may if desired also comprisefurther additives, examples being antioxidants, light stabilizers, metaldeactivators, antistatic agents, flame retardants, lubricants,nucleating agents, acid scavengers (basic costabilizers), pigments andfillers. Examples of suitable additives which can additionally beemployed in combination are compounds, as set out below:

[0170] 1. Antioxidants

[0171] 1.1 Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, linear or sidechain-branchednonylphenols, such as 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1-methylundec-1′-yl)-phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)-phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

[0172] 1.2 Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol.

[0173] 1.3 Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0174] 1.4 Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide.

[0175] 1.5 Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclo-hexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidene-bis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,bis(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)-pentane, ethyleneglycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate].

[0176] 1.6 O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, tridecyl4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate.

[0177] 1.7 Hydroxybenzylated malonates, for example dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecyl-mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,di-[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0178] 1.8 Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-phenol.

[0179] 1.9 Triazine compounds, for example2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0180] 1.10 Benzylphosphonates, for example dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, theCa-salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0181] 1.11 Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0182] 1.12 Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalamide,3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0183] 1.1 Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalamide,3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0184] 1.14 Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalamide,3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0185] 1.15 Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxalamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0186] 1.16 Esters of 3,3-bis(3′tert-butyl-4′-hydroxyphenyl)butyric acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxalamide,3-thia-un-decanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0187] 1.17 Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid, e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

[0188] 1.18 Tocopherol, such as α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0189] 1.19 Ascorbic acid (vitamin C).

[0190] 1.20 Amine antioxidants, for exampleN,N′-diisopropyl-p-phenylenediamine,N,N′di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-di(naphthyl-2-)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(-toluenesulfonamido)diphenylamine,N,N′-di-methyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, e.g.p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, di(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-di-[(2-methylphenyl)amino]ethane, 1,2-di-(phenylamino)propane,(o-tolyl)biguanide, di[4-(1′,3′-dimethylbutyl)-phenyl]-amine,tert-octylated N-phenyl-1-naphthylamine, mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, mixture of mono- anddialkylated nonyldiphenylamines, mixture of mono- and dialkylateddodecyldiphenylamines, mixture of mono- and dialkylatedisopropyl/isohexyl-diphenylamines, mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexamethylenediamine,bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidine-4-ol.

[0191] 2. UV Absorbers and Light Stabilizers

[0192] 2.1 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzogtriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-[2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotrazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the transesterification product of2-[3′-tert.-butyl-5′-(2-methoxycarbonylethyl)-2′-hydrqxyphenyl]benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—(CH₂)₃]₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl-phenyl.

[0193] 2.2 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and2′-hydroxy-4,4′-di-methoxy derivative.

[0194] 2.3 Esters of substituted or unsubstituted benzoic acids, forexample 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

[0195] 2.4 Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate orisooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxycinnamate or butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-p-cyano-vinyl)-2-methylindoline.

[0196] 2.5 Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

[0197] 2.6 Sterically hindered amines, for examplebis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate,bis(2,2,6,6-tetramethylpiperidine-4-yl)glutarate,bis(2,2,6,6-tetramethylpiperidine-4-yl)succinate,bis(1,2,2,6,6-pentamethylpiperidine-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidine-4-yl)glutarate,2,2,6,6-tetramethylpiperidyl behenate,1,2,2,6,6-pentamethylpiperidyl-behenate, the condensate of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylendiamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrilo-triacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butantetraoate,1,1′-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,4-stearoyloxy-2,2,6,6-tetramethylpiperidine,4-stearyloxy-1,2,2,6,6-pentamethylpiperidine,4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,bis(1,2,2,6,6-pentamethylpiperidyl)2-n-butyl-2-(4-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5] decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpipenidyl)sebacate,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensateof N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-methoxypropylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-methoxypropylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)-ethane, reaction products of2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazinewith mono- or polyfunctional amines, where between one and all theactive hydrogen atoms on the amine are replaced, such as withethylenediamine, diethylenetriamine, triethylenetetramine,hexamethylenediamine, 1,2-bis-(3-aminopropylamino)ethane, reactionproducts of2-chloro-4,6-di-(4-n-butyl-amino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazinewith mono- or polyfunctional amines, where between one and all theactive hydrogen atoms on the amine are replaced, such as withethylenediamine, diethylenetriamine, triethylenetetramine,hexamethylenediamine, 1,2-bis(3-aminopropylamino)ethane, reactionproducts of2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine with mono- orpolyfunctional amines, where between one and all the active hydrogenatoms on the amine are replaced, such as with ethylenediamine,diethylenetriamine, triethylenetetramine, haxamethylenediamine,1,2-bis(3-aminopropylamino)ethane, reaction products of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine with mono- orpolyfunctional amines, where between one and all the active hydrogenatoms on the amine are replaced, such as with ethylenediamine,diethylenetriamine, triethylenetetramine, hexa nethylenediamine,1,2-bis-(3-aminopropyl-amino)ethane, reaction products of2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand4-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-2,6-dichloro-1,3,5-s-triazinewith mono- or polyfunctional amines, where between one and all theactive hydrogen atoms on the amine are replaced, such as withethylenediamine, diethylenetriamine, triethylenetetramine,hexamethylenediamine, 1,2-bis-(3-aminopropyl-amino)ethane, reactionproducts of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand4-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-2,6-dichloro-1,3,5-s-triazinewith mono- or polyfunctional amines, where between one and all theactive hydrogen atoms on the amine are replaced, such as withethylenediamine, diethylenetriamine, triethylenetetramine,hexamethylenediamine, 1,2-bis-(3-aminopropylamino)ethane, the condensateof 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazineand also 4-butylamino-2,2,6,6-tetramethylpiperidine,N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,oligomerized2,2,4,4-tetramethyl-20-(oxiranylmethyl)-7-oxa-3,20-diaza-di-spiro[5.1.11.2]heneicosan-21-one,oligomerized1,2,2,4,4-pentamethyl-20-(oxiranylmethyl)-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one,oligomerized1-acetyl-2,2,4,4-tetramethyl-20-(oxiranylmethyl)-7-oxa-3,20-diaza-dispiro-[5.1.11.2]heneicosan-21-one,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]heneicosan-21-one,2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diazadispiro-[5.1.11.2]heneicosane-3-propanoicacid dodecyl ester,2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diaza-dispiro-[5.1.11.2]heneicosane-3-propanoicacid tetradecyl ester,2,2,3,4,4-penta-methyl-7-oxa-3,20-diazadispiro-[5.1.11.2]heneicosan-21-one,2,2,3,4,4-pentamethyl-7-oxa-21-oxo-3,20-diaza-dispiro-[5.1.11.2]heneicosane-3-propanoicacid dodecyl ester,2,2,3,4,4-pentamethyl-7-oxa-21-oxo-3,20-diazadispiro-[5.1.11.2]-henelicosane-3-propanoicacid tetradecyl ester,3-acetyl-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]heneicosane-21-one,3-acetyl-2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diaza-dispiro-[5.1.11.2]heneicosane-3-propanoicacid dodecyl ester,3-acetyl-2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diazadispiro-[5.1.11.2]heneicosane-3-propanoicacid tetradecyl ester,1,1′,3,3′,5,5′-hexahydro-2,2′,4,4′,6,6′-hexaaza-2,2′,6,6′-bismethano-7,8-dioxo-4,4′-bis(1,2,2,6,6-pentamethyl-4-piperidyl)biphenyl,poly-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,8-diazadecylene,adduct of 2,2,6,6-tetramethyl-4-allyloxypiperidine andpolymethylhydridosiloxane (molar mass up to 4000), adduct of1,2,2,6,6-pentamethyl-4-allyloxypiperidine and polymethylhydridosiloxane(molar mass up to 4000),N,N′-diformyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine,N,N′-diformyl-N,N′-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)hexamethylenediamine,5,11-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-3,5,7,9,11,13-hexaazatetra-cyclo-[7.4.0.0^(2,7).1^(3,13)]tetradecane-8,14-dione,5,11-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-3,5,7,9,11,13-hexaazatetra-cyclo[7.4.0.0^(2,7).1^(3,13)]tetradecane-8,14-dione,[(4-methoxyphenyl)methylene]-propanedioic acidbis(2,2,6,6-tetramethyl-4-piperidinyl) ester,[(4-methoxyphenyl)-methylene]propanedioic acidbis-(1,2,2,6,6-pentamethyl-4-piperidinyl) ester,2,4,6-tris(N-cyclohexyl-N-[2-(3,3,4,5,5-pentamethylpiperazinon-1-yl)ethyl]amino)-1,3,5-triazine,copolymer of styrene with methylstyrene and maleic anhydride reactedwith 4-amino-2,2,6,6-tetramethyl-piperidine and octadecylamine,copolymer of styrene with α-methylstyrene and maleic anhydride reactedwith 4-amino-1,2,2,6,6-pentamethylpiperidine and octadecylamine,polycarbonate with2,2′-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-bis[ethanol] as diolcomponent, polycarbonate comprising2,2′-(1,2,2,6,6-pentamethyl-4-piperidinyl)imino]bis[ethanol] as diolcomponent, copolymer of maleic anhydride and an α-olefin up to C₃₀reacted with 4-amino-2,2,6,6-tetramethyl-piperidine, copolymer of maleicanhydride and an α-olefin up to C₃₀ reacted with1-acetyl-4-amino-2,2,6,6-tetramethylpiperidine, copolymer of maleicanhydride and an α-olefin up to C₃₀ reacted with4-amino-1,2,2,6,6-pentamethylpiperidine, and also the N-alkyl- andN-aryl-oxy derivatives of the abovementioned compounds with free NHgroups on the piperidine, especially α-methylbenzyloxy and alkyloxy fromC₁ to C₁₈.

[0198] 2.7 Oxalamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyanilide, 2,2′-dioctyloxy-5,5′-di-tert-butyloxanilide,2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of o- andp-methoxy-disubstituted and of o- and p-ethoxy-disubstituted oxanilides.

[0199] 2.8 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4′,6-bis(2′,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

[0200] 3. Metal deactivators, for example, N,N′-diphenyloxalamnide,N-salicylal-N′-salicyclohydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl-hydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0201] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bisisodecyloxy pentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite,bis(2,4,6-tri-tert-butyl-phenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-blutylphenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin,bis(2,41-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,tris(2-tert-butyl-4-thio(2′-methyl-4′-hydroxy-5′-tert-butyl)phenyl-5-methyl)phenyl phosphite, 2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],bis[2-methyl-4,6-bis(1,1-dimethylethyl)phenol]phosphorous acid ethylester.

[0202] 5. Hydroxylamines, examples being N,N-dibenzylhydroxylamine,N,N-diethyl-hydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-di-tetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylaminesprepared from hydrogenated tallow fatty amine.

[0203] 6. Nitrones, examples being N-benzyl alpha-phenyl nitrone,N-ethyl alpha-methyl nitrone, N-octyl alpha-heptyl nitrone, N-laurylalpha-undecyl nitrone, N-tetradecyl alpha-tridecyl nitrone, N-hexadecylalpha-pentadecyl nitrone, N-octadecyl alpha-heptadecyl nitrone,N-hexadecyl alpha-heptadecyl nitrone, N-octadecyl alpha-pentadecylnitrone, N-heptadecyl alpha-heptadecyl nitrone, N-octadecylalpha-hexadecyl nitrone, nitrones derived from N,N-dialkylhydroxylaminesprepared from hydrogenated tallow fatty amines.

[0204] 7. Zeolites and hydrotalcites, such as ®DHT 4A. Hydrotalcites ofthis kind can be described by the formula

[(M²⁺)_(1−x)(M³⁺)_(x)(OH)₂(A^(n−))_(x/n) yH₂O],

[0205] where

[0206] (M²⁺) is Mg, Ca, Sr, Ba, Zn, Pb, Sn, Ni

[0207] (M³⁺) is Al, B, Bi

[0208] A^(n) is an anion of valency n

[0209] n is an integer from 1-4

[0210] x is a value between 0 and 0.5

[0211] y is a value between 0 and 2

[0212] A is OH⁻, Cl⁻, Br⁻, I⁻, ClO₄—, CH₃COO⁻, C₆H₅COO⁻, CO₃ ²⁻, SO₄ ²⁻,(OOC—COO)²⁻, (CHOHCOO)₂ ²⁻, (CHOH)₄CH₂OHCOO⁻, C₂H₄(COO)₂ ²⁻, (CH₂COO)₂²⁻, CH₃CHOHCOO⁻, SiO₃ ²⁻, SiO₄ ⁴⁻, Fe(CN)₆ ³⁻, Fe(CN)₆ ⁴⁻, BO₃ ³⁻, PO₃³⁻, HPO₄ ²⁻.

[0213] Preference is given to employing hydrotalcites in which (M²⁺) is(Ca²⁺), (Mg²⁺) or a mixture of (Mg²⁺) and (Zn²⁺); (A^(n−)) is CO₃ ²⁻,BO₃ ³⁻, PO₃ ³⁻; x has a value from 0 to 0.5 and y has a value from 0 to2. It is also possible to employ hydrotalcites that can be describedwith the formula

[(M²⁺)_(x)(Al³⁺)₂(OH)_(2x+6nz)(A^(n−))₂ yH₂O].

[0214] Here (M²⁺) is Mg²⁺, Zn²⁺, but more preferably Mg²⁺. (A^(n−)) isan anion, in particular from the group consisting of CO₃ ²⁻,(OOC—COO)²⁻, OH⁻ and S²⁻, where n describes the valency of the ion. y isa positive number, more preferably between 0 and 5, especially between0.5 and 5. x and z have positive values, which in the case of x arepreferably between 2 and 6 and in the case of z should be less than 2.The hydrotalcites of the following formulae are to be regarded withparticular preference:

Al₂O₃×6MgO×CO₂×12H₂O,

Mg_(4.5)Al₂(OH)₁₃×CO₃×3.5H₂O,

4MgO×Al₂O₃×CO₂×9H₂O,

4MgO×Al₂O₃×CO₂×6H₂O,

ZnO×3MgO×Al₂O₃×CO₂×8-9H₂O,

ZnO×3MgO×Al₂O₃×CO₂×5-6H₂O,

Mg_(4.5)Al₂(OH)₁₃×CO₃.

[0215] Hydrotalcites are employed in the polymer preferably in aconcentration of from 0.01 to 5% by weight, in particular from 0.2 to 3%by weight, based on the overall polymer formulation.

[0216] 8. Thiosynergists, examples being dilauryl thiodipropionate anddistearyl thiodipropionate.

[0217] 9. Peroxide scavengers, examples being esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl ester, mecaptobenzimidazole, the zinc salt of2-mercaptobenzimidazole, zinc alkyldithiocarbamates, zincdibutyldithiocarbamate, dioctadecyl monosulfide, dioctadecyl disulfide,pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0218] 10. Polyamide stabilizers, examples being copper salts incombination with iodides and/or phosphorus compounds and salts ofdivalent manganese.

[0219] 11. Basic costabilizers, examples being melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamines, polyurethanes,alkali metal and alkaline earth metal salts of higher fatty acids, forexample Ca stearate, Zn stearate, Mg behenate, Mg stearate, Naricinoleate, K palmitate, antimony pyrocatecholate or tinpyrocatecholate, alkali metal and alkaline earth metal salts and alsothe zinc salt or the aluminum salt of lactic acid.

[0220] 12. Nucleating agents, such as inorganic substances, examplesbeing talc, metal oxides, such as titanium oxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals, organic compounds, such as mono- or polycarboxylic acids andalso their salts, examples being 4-tert-butylbenzoic acid, ladipic acid;diphenylacetic acid; sodium succinate or sodium benzoate; acetals ofaromatic aldehydes and polyfunctional alcohols such as sorbitol, forexample, such as 1,3-2,4-di(benzylidene)-D-sorbitol,1,3-2,4-di(4-tolylidene)-D-sorbitol,1,3-2,4-di(4-ethylbenzylidene)-D-sorbitol, polymeric compounds, such asionic copolymers (ionomers), for example.

[0221] 13. Fillers and reinforcing agents, examples being calciumcarbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and metal hydroxides, carbon black, graphite, woodflour and other flours or fibers of other natural products, syntheticfibers.

[0222] 14. Other additives, examples being plasticizers, lubricants,emulsifiers, pigments, rheological additives, catalysts, levelingassistants, optical brighteners, flame-proofing agents, antistatics,blowing agents, color improvers.

[0223] 15. Benzofuranones and indolines, as described for example inU.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No.5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643,DE-A4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102,or 3-[4-(2-acetoxy-ethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuranon-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-one,5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-diethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one.

[0224] The invention relates also to those of the mentioned additives,which are used in form of nano-sized particles.

[0225] The following examples shall demonstrate the invention.

EXAMPLES

[0226] The following compounds have been used:

[0227] compound (a): Sandostab P-EPQ® (Clariant)

[0228] tetrakis(2,4-di-tert.-butylphenyl)-4,4′-biphenylendiphosphit

[0229] compound (b): 5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one

[0230] compound (c): Hostavin N30® (Clariant)

[0231] polymer of epichlorhydrin and2,2,4,4-tetramethyl-7-oxa-3,20-diaza-20-(2,3-epoxi-propyl)-dispiro-[5.1.11.2]-heneicosane-21-one

[0232] compound (d): Hostanox O 10® (Clariant)

[0233]tetrakis[methylen-3-(3′,5′)-di-tert.-butyl-4′-hydroxyphenyl)propionate]methane

[0234] Tinuvin 622® (Ciba SC):

[0235]poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl-succinate)

[0236] In the following description “parts” mean “parts by weight”.

[0237] Polypropylene 3^(rd) generation (type Moplen FL F20; producerMontell; melt flow (230° C./2.16 kg):14.2 g/10 min.) has been processedby multiple pass extrusion at T=280° C. after adding to 100 parts of thepolymer 0.025 parts triphenylphosphine, 0.025 parts compound (b), 0.020%compound (c) and 0.10 parts Ca-stearate.

[0238] The polymer powder and the additives have been mixed andhomogenized in a laboratory mixer type Kenwood before pre-extrusion wascarried out using a single screw extruder type KPS-25 (producer Haendle;screw diameter 4mm) at 210° C./80 rpm. The main extrusions took placeusing a single screw extruder type Göttfert Extrusimeter at T=280° C.(screw-compression 1:3, 50 rpm, die-diameter 2 mm) coupled with anonline-rheometer. The individual melt flow indices have been determinedaccording to ASTM 1238 at 230° C./2.16 kg). Color has been measuredaccording to DIN 6167 using a Minolta spectrocolorimeter. Thecorresponding results are listed in the following tables 1A and 1B andcompared against a formulation which contains 0.10 parts compound (d)(tetrafunctional, commercial phenol), 0.05 parts compound (a) and 0.10parts Ca-stearate. TABLE 1A MFI-results stabilizer formulation (acidscavenger: 0.10% Ca-stearate) 1^(st) pass 3^(rd) pass 5^(th) passcomparative:  0.05 parts compound (a) + 13.22 16.85 22.27  0.10 partscompound (d) 0.025 parts triphenylphosphine + 12.81 15.48 18.20 0.025parts compound (b) +  0.02 parts compound (c)

[0239] TABLE 1B Color (YI) stabilizer formulation (acid scavenger: 0.10%Ca-stearate) 1^(st) pass 3^(rd) pass 5^(th) pass comparative: 0.05 partscompound (a) + 1.49 2.77 4.78 0.10 parts compound (d) 0.025 partstriphenylphosphine + 0.27 0.51 1.34 0.025 parts compound (b) + 0.02parts compound (c)

Processing, Exposure and Testing of Polypropylene

[0240] 100 parts by weight of polypropylene (PP), type Moplen FLF20(producer: Himont; internal code PP 97-4) [MFI: 12 g/10 min/230° C./2.16kg] has been mixed in a laboratory mixer from Kenwood adding 0.10 partsby weight of Hostanox O 10® (phenol), 0.10 parts by weight ofCa-stearate, 0.05 parts by weight of Sandostab P-EPQ®. After processingthis sample has been taken as reference. Alternatively used formulationsbased on 0.02 parts by weight of a sterically hindered amine (HA(L)S),0.10 parts by weight of Ca-stearate, 0.04 parts by weight of5,7-di-tert.-butyl-(3-phenyl)-3H-benzofuran-2-one (lactone) and 0.01parts by weight of triphenylphosphine. Afterwards pre-extrusion wascarried out using a single screw extruder type Haendle KPS 25 (screwcompression 1:3, die diameter 4 mm, screw speed 80 rpm) at 220° C. Themain extrusions (1^(st)-5^(th)) took place using a single screw extrudertype Göttfert Extrusimeter (screw-compression 1:3, 100 rpm, die-diameter2 mm) with 1 heating zone at 180° C., 2 heating zones at 200° C. and 4heating zones each at T=210° C. This process step was finalized bygranulation (0.5-2.00 mm). Granules of the 1^(st) and 5^(th) extrusionpass have been lateron transferred into the frame (thickness 0.5 mm)placed on a laboratory heat press type Fontjne TP 600. The platetemperature of 210° C. was chosen applying first during a period of 90seconds a pressure of 50 kN, afterwards for another 90 seconds apressure of 500 kN.

[0241] The so prepared plates have been used for artificial long-termexposure (CAM-7) using a Xe-Arc-type Weatherometer according to theprocedure described under ASTM G 26-90. As an important feature thedevelopment of the carbonyl-absorption as measured by means of anIR-spectrometer type FTS 155 has been chosen which describes therelative extent of degradation by oxidation. This method is primarilyintended for polypropylene. Actual measurements concentrate on theresidence time (in hours) to develop a carbonyl-absorption Δ (>C═O)=1.Measured were samples after the first and the fifth extrusion pass. Theresults are presented in Table 2. Supplementary to the given time valueto reach an additional carbonyl-absorption Δ (>C═O)=1 a prolongationfactor PF is shown which reflects the efficiency of the individualstabilzer system as well.

[0242] As longer the measured time period and as larger thisprolongation factor as better efficiency is provided by the stabilizersystem.

[0243] According to data given in Table 2 it clearly can be demonstratedthat the formulation consisting of 0.01% triphenylphosphine, 0,04%5,7-di-tert.-butyl-(3-phenyl)-3H-benzofuran-2-one (in Table 2 referredto as “lactone”) and 0.02% Hostavin N 300 outperforms the otherformulation and is particularly superior to the (traditional)phenol-containing formulation (reference). TABLE 2 extrusion stabilizerdelta (>C═O) = prolongation pass no. formulation 1/hrs. factor 1 0.05%Sandostab 317 1 P-EPQ ®, 0.10% Hostanox O 10 ® (Reference) 5 0.05%Sandostab 293 1 P-EPQ ®, 0.10% Hostanox O 10 ® (Reference) 1 0.01%triphenylphosphine, 911 2.874 0.04% lactone, 0.02% Tinuvin 622 ® 5 0.01%triphenylphosphine, 868 2.962 0.04% lactone, 0.02% Tinuvin 622 ® 1 0.01%triphenylphosphine, 1098 3.464 0.04% lactone, 0.02% Hostavin N 30 ® 50.01% triphenylphosphine, 1149 3.921 0.04% lactone, 0.02% Hostavin N30 ®

1. A stabilizer composition for thermoplastic polymers comprising a) atleast one organophosphine, b) at least one 2-phenylbenzofuranone, and c)at least one sterically hindered piperidine based stabilizer (HAS),wherein the weight ratio of component a) to component b) to component c)is from 1:0.05:0.5 to 1:3:5.
 2. A stabilizer composition as claimed inclaim 1, comprising a) at least one compound of the formulae (I) to (IV)

 in which independently of one another R₁ is C₁₋₂₄-alkyl orC₁₋₂₄-N,O,P,S-heteroalkyl; C₅₋₃₀-cycloalkyl orC₅₋₃₀-N,O,P,S-heterocycloalkyl; C₇₋₃₀-alkylaryl; C₆₋₂₄-aryl;C₄₋₂₄-N,O,P,S-heteroaryl; C₆₋₂₄-aryl or C₄₋₂₄-N,O,P,S-heteroaryl mono-or poly-substituted by C₁₋₁₈-alkyl, C₅₋₁₂-cycloalkyl or by C₁₋₁₈-alkoxygroups; R₂ is C₄₋₂₄-alkyl or C₄₋₂₄-N,O,P,S-heteroalkyl; C₅₋₃₀-cycloalkylor C₅₋₃₀-N,O,P,S-heterocycloalkyl; C₇₋₃₀-alkylaryl; C₆₋₂₄-aryl;C₄₋₂₄-N,O,P,S-heteroaryl; C₆₋₂₄-aryl or C₄₋₂₄-N,O,P,S-heteroaryl mono-or poly-substituted by C₁₋₁₈-alkyl, by C₅₋₁₂-cycloalkyl or byC₁₋₁₈-alkoxy groups; D is C₁₋₃₀-alkylene or C₁₋₃₀-N,O,P,S-alkylene,linear or branched; C₂₋₃₀-alkylidene or C₂₋₃₀-N,O,P,S-alkylidene;C₅₋₁₂-cycloalkylene or C₅₋₁₂-N,O,P,S-cycloalkylene; C₆₋₂₄-arylene orC₄₋₂₄-N,O,P,S-heteroarylene, unsubstituted or one- or morefoldsubstituted by linear or branched C₁₋₁₈-alkyl, by C₅₋₁₂-cycloalkyl or byC₁₋₁₈-alkoxy; or —O—, —S—; q is 1 to 5; r is 3 to 6, where the groupsP—R₁ in the formula (IV) are a component of a phosphacycle, indicatedby * in the bonds originating from P; b) at least one compound of theformula V

 in which R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h)independently of one another are hydrogen; hydroxyl; C₁-C₁₈-alkyl; orphenyl which is unsubstituted or mono-, di- or trisubstituted byC₁-C₄-alkyl; are C₇-C₉-phenylalkyl, C₁-C₁₈-alkoxy or C₅-C₁₂-cycloalkylunsubstituted or mono-, di- or trisubstituted by C₁-C₄-alkyl; and R^(c)has one of the meanings given above for R^(a), R^(b), R^(d), R^(e),R^(f), R^(g) and R^(h) or is a radical of the formula (VI)

 in which R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) are asdefined above and R^(i) and R^(j) independently of one another arehydrogen or C₁-C₄-alkyl, where at least two of the radicals R^(d),R^(e), R^(f), R^(g) and R^(h) are hydrogen; and c) at least onesterically hindered amine of the formula VII,

 in which X₁ is hydrogen; a C₁-C₂₂-alkyl group; an oxygen radical O*;—OH; —NO; —CH₂CN; benzyl; allyl; a C₁-C₃₀-alkoxy group; aC₅-C₁₂-cycloalkyloxy group; a C₆-C₁₀-aryloxy group; aC₇-C₂₀-arylalkyloxy group or a C₇-C₂₀-arylalkyloxy group where the arylradical is substituted by a C₁-C₅-alkyl group or a halogen or a nitrogroup; a C₃-C₁₀-alkenyl group; a C₃-C₆-alkinyl group; a C₁-C₁₀-acylgroup; halogen; an unsubstituted or C₁-C₄-alkyl-substituted phenylradical; X₂ is hydrogen; a [CH₂—CH₂—C(O)—O—X₅] radical; a[CH₂—C(CH₃)H—C(O)—O—X₅] radical; a C₁-C₂₂-alkyl group; X₃ and X₄independently of one another are hydrogen; an unsubstituted orC₁-C₄-alkyl-substituted phenyl radical; or a C₁-C₂₂-alkyl group, whereat least one of the two radicals X₃ and X₄ is a branched C₄-C₂₂-alkylgroup; and in which X₅ is a C₁-C₂₂-alkyl group.
 3. A stabilizercomposition as claimed in claim 1 or 2, wherein R₁ is C₈₋₂₄-alkyl orC₈₋₂₄-N,O,P,S-heteroalkyl; C₆₋₁₂₋cycloalkyl orC₆₋₁₂-N,O,P,S-heterocycloalkyl; C₇₋₂₄-alkylaryl; C₆₋₁₆-aryl;C₄₋₁₈-N,O,P,S-heteroaryl; C₆₋₁₆-aryl or C₄₋₁₈-N,O,P,S-heteroaryl mono-or polysubstituted by C₁₋₁₂-alkyl, by C₅₋₈-cycloalkyl or by C₁₋₁₂-alkoxygroups; R₂ is C₆₋₁₈-alkyl or C₆₋₁₈-N,O,P,S-heteroalkyl; C₅₋₁₂-cycloalkylor C₅₋₁₂-N,O,P,S-heterocycloalkyl; C₇₋₁₈-alkylaryl; C₆₋₁₆-aryl;C₄₋₁₈-N,O,P,S-heteroaryl; C₆₋₁₆-aryl or C₄₋₁₈-N,O,P,S-heteroaryl mono-or polysubstituted by C₁₋₁₂-alkyl, by C₅₋₈-cycloalkyl or by C₁₋₁₂-alkoxygroups; D is C₁₋₂₄-alkylene or C₁₋₂₄-N,O,P,S-alkylene, linear orbranched; C₂₋₂₄-alkylidene or C₂₋₂₄-N,O,P,S-alkylidene;C₅₋₈-cycloalkylene or C₅₋₈-N,O,P,S-cycloalkylene; C₆₋₂₄-arylene orC₄₋₁₈-N,O,P,S-heteroarylene, unsubstituted or one- or morefoldsubstituted by linear or branched C₁₋₁₈-alkyl, by C₅₋₈-cycloalkyl or byC₁₋₁₂-alkoxy; or —O—; —S—; q is 1 to 4; r is 4 or 5, where the groupsP—R₁ in the formula (IV) are component of a phosphacycle, indicated by *in the bonds originating from P; R^(a), R^(b), R^(d), R^(e), R^(f),R^(g) and R^(h) independently of one another are hydrogen; hydroxyl;C₁-C₁₂-alkyl; or phenyl which is unsubstituted or mono-, di- ortrisubstituted by C₁-C₂-alkyl; are C₇-C₉-phenylalkyl; C₁-C₁₂-alkoxy orC₅-C₈-cycloalkyl unsubstituted or mono-, di- or trisubstituted byC₁-C₂-alkyl; and R^(c) has one of the meanings given above for R^(a),R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) or is a radical of the;formula (VI) in which R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h)are as defined above and R^(i) and R^(j) independently of one anotherare hydrogen or C₁-C₂-alkyl, where at least two of the radicals R^(d),R^(e), R^(f), R^(g) and R^(h) are hydrogen; X₁ is hydrogen; aC₁-C₅-alkyl group; an oxygen radical O*; —OH; —NO; —CH₂CN; benzyl;allyl; a C₁-C₁₀-alkoxy group; a C₅-C₆-cycloalkyloxy group; aC₆-C₇-aryloxy group; a C₇-C₁₀-arylalkyloxy group or aC₇-C₁₀-arylalkyloxy group where the aryl radical is substituted by aC₁-C₅-alkyl group or a halogen or a nitro group; a C₃-C₆-alkenyl group;a C₃-C₆-alkinyl group; a C₁-C₅-acyl group; halogen; an unsubstituted orC₁-C₂-alkyl-substituted phenyl radical; X₂ is hydrogen; a[CH₂—CH₂—C(O)—O—X₅] radical; a [CH₂—C(CH₃)H—C(O)—O—X₅] radical; aC₁-C₁₀-alkyl group; X₃ and X₄ independently of one another are hydrogen;an unsubstituted or C₁-C₂-alkyl-substituted phenyl radical or a branchedC₄-C₂₂-alkyl group, where at least one of the two radicals X₃ and X₄ isa branched C₄-C₁₀-alkyl group; and in which X₅ is a C₁₀-C₁₆-alkyl group.4. A stabilizer composition as claimed in claim 1, wherein R₁ isC₁₂₋₁₆-alkyl or C₁₂₋₁₆-N,O,P,S-heteroalkyl; C₆₋₈-cycloalkyl orC₆₋₈-N,O,P,S-heterocycloalkyl; C₇₋₁₂-alkylaryl; C₆₋₁₂-aryl orC₄₋₁₀-N,O,P,S-heteroaryl; C₆₋₁₂-aryl or C₄₋₁₀-heteroaryl mono- orpolysubstituted by C₁₋₁₈-alkyl, by C₅₋₆-cycloalkyl or by C₁₋₈-alkoxygroups; R₂ is C₈₋₁₈-alkyl or C₈₋₁₈-N,O,P,S-heteroalkyl; C₅₋₈-cycloalkylor C₅₋₈-N,O,P,S-heterocycloalkyl; C₇₋₁₂-alkylaryl; C₆₋₁₂-aryl;C₄₋₁₀-N,O,P,S-heteroaryl; C₆₋₁₂-aryl or C₄₋₁₀-N,O,P,S-heteroaryl mono-or polysubstituted by C₁₋₈-alkyl, by C₅₋₆-cycloalkyl or by C₁₋₈-alkoxygroups; D is C₁₋₁₈-alkylene or C₁₋₁₈-N,O,P,S-alkylene, linear orbranched; C₂₋₁₈-alkylidene or C₂₋₁₈-N,O,P,S-alkylidene;C₅₋₈-cycloalkylene or C₅₋₈-N,O,P,S-cycloalkylene; C₆₋₁₈-arylene orC₄₋₁₈-N,O,P,S-heteroarylene, unsubstituted or one- or morefoldsubstituted by linear or branched C₁₋₁₂-alkyl, by C₅₋₈-cycloalkyl or byC₁₋₈-alkoxy; or —O—; —S—; q is 1 to 3; r is 4 or 5, where the groupsP—R₁ in the formula (IV) are component of a phosphacycle, indicated by *in the bonds originating from P, R^(a), R^(b), R^(d), R^(e), R^(f),R^(g) and R^(h) independently of one another are hydrogen; hydroxyl;C₁-C₆-alkyl; or phenyl which is unsubstituted or mono-, di- ortrisubstituted by C₁-C₂-alkyl; are C₇-C₉-phenylalkyl; C₁-C₆-alkoxy orC₅-C₈-cycloalkyl unsubstituted or mono-, di- or trisubstituted byC₁-C₂-alkyl; and R^(c) has one of the meanings given above for R^(a),R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h) or is a radical of theformula (VI) in which R^(a), R^(b), R^(d), R^(e), R^(f), R^(g) and R^(h)are as defined above and R^(i) and R^(j) independently of one anotherare hydrogen or C₁-C₂-alkyl, where at least two of the radicals R^(d),R^(e), R^(f), R^(g) and R^(h) are hydrogen; X₁ is hydrogen; a methylgroup; an oxygen radical O*; —OH; —NO; —CH₂CN; benzyl; allyl; aC₁-C₆-alkoxy group; a C₅-C₆-cycloalkyloxy group; a C₆-aryloxy group; aC₃-C₆-alkenyl group; a C₃-C6-alkinyl group; a C₁-C₅-acyl group; halogen;an unsubstituted or C₁-C₂-alkyl-substituted phenyl radical; X₂ ishydrogen, a [CH₂—CH₂—C(O)—O—X₅] radical, a [CH₂—C(CH₃)H—C(O)—O—X₅]radical, a C₁-C₄-alkyl group; X₃ and X₄ independently of one another arehydrogen, an unsubstituted or C₁-C₂-alkyl-substituted phenyl radical ora branched C₄-C₆-alkyl group, where at least one of the two radicals X₃and X₄ is a branched C₄-C₆-alkyl group; and in which X₅ is aC₁₂-C₁₄-alkyl group.
 5. A stabilizer composition as claimed in any ofclaims 1 to 4, comprising a) triphenylphosphine, b)2-phenylbenzofuranone and c) polymer of epichlorhydrin and2,2,4,4-tetramethyl-7-oxa-3,20-diaza-20-(2,3-epoxi-propyl)-dispiro-[5.1.11.2]-heneicosane-21-one,wherein the weight ratio of component a) to component b) to component c)is from 1:0.1:1 to 1:1:3.
 6. Process of stabilizing thermoplasticpolymers by incorporating a stabilizer composition as claimed in any ofclaims 1 to 5 in an amount of from 0.01 to 1% by weight into the polymerto be stabilized.